Cyclopropyl phosphates and phosphonates



United States Patent (3' 3,485,899 CYCLOPROPYL PHOSPHATES AND PHOSPHONATES Gerald H. Peterson, West Los Angeles, Calif. (12612 Preston Way, Los Angeles, Calif. 90066) No Drawing. Filed May 15, 1967, Ser. No. 638,567 Int. Cl. C07f 9/12, 9/40; C10m 3/40 US. Cl. 260958 14 Claims ABSTRACT OF THE DISCLOSURE This invention relates to new chemical compounds which are phosphate esters and phosphonate esters having three organic radicals at least one of which is the cyclopropyl radical and the other organic radicals of which are the cyclopropyl radical, the phenyl radical, or the tolyl radical.

Dicyclopropyl cyclopropane phosphonate Herein CP stands for the cyclopropyl radical.

Diphenyl cyclopropane phosphonate Herein Ph stands for the phenyl radical.

Dimetatolyl cyclopropane phosphonate Herein T stands for the tolyl radical and generically designates ortho, meta, and para tolyl and mixtures thereof.

3,485,899 Patented Dec. 23, 1969 ice Cyclopropyl metatolyl cyclopropane phosphonate OP O=I"-O-Tm 6P Herein Tm designates the metatolyl radical.

Cyclopropyl phenyl cyclopropane phosphonate OP o=i*0-c1 Dicyclopropyl benzene phosphonate Ph o=i o-oP I C P Dicyclopropyl toluene phosphonate Cyclopropyl phenyl benzene phosphonate Cyclopropyl metatolyl benzene phosphonate Ph O=l ?OTn1 Cyclopropyl tolyl toluene phosphonate Tm O =I OTu1 IJP Cyclopropyl phenyl toluene phosphonate Tm O=] ?OIh In Tolyl phenyl cyclopropane phosphonate OP O=l ?OTm Each of these new foregoing chemical compounds can be made by the same methods used for making the corresponding phosphates and phosphonates where the propyl radical is used instead of the cyclopropyl radical. The methods of making the corresponding phosphates and phosphonates with the propyl radical are known to those skilled in the art, and with the disclosure herein those skilled in the art to which my invention appertains will be able to make and use the new chemical compounds of my invention.

The preparation of the known phosphate esters and phosphonate esters having thepropyl radical instead of the cyclopropyl radical of my invention is disclosed in the books entitled Introduction to Hydraulic Fluids" by Roger E. Hatton, published by Rheingold Publishing Corporation and Organo-Phosphorous Compounds by G. M. Kosolopoff, published by John Wiley and Sons, and numerous other publications and issued patents. The particular relevant disclosure in the book entitled Introduction to Hydraulic Fluids appears on pages 190 through 195.

Even though those skilled in the art will be able to prepare and use the new chemical compounds of my invention, there is given below examples of these compounds and their preparation.

EXAMPLE 1 Tricyclopropyl phosphate 3.5 mols of cyclopropyl alcohol are added dropwise with stirring to one mol of phosphorus oxychloride (POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and tricyclopropyl phosphate is collected.

EXAMPLE 2 Tricyclopropyl phosphate To 5 mols of cyclopropauol, three mols of freshly cut metallic sodium are added in small cubes about A" with stirring and maintaining the temperature between 25 and 40 C. When reaction is complete as evidenced by cessation of bubbling, one mol of phosphorus oxychloride (POCl is added dropwise with stirring while maintaining the temperature at about 25-50 C. The reaction mixture is filtered to remove the precipated sodium chloride and the filtrate is distilled and tricyclopropyl phosphate is collected.

EXAMPLE 3 Dicyclopropyl phenyl phosphate Two mols of cyclopropanol are added dropwise with stirring to one mol of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mum/Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at -5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble dicyclopropyl phenyl phosphate.

EXAMPLE 4 Dicyclopropyl tolyl phosphate Two mols of cyclopropanol are added dropwise with stirring to one mol of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of metacresol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble dicyclopropyl metatolyl phosphate.

EXAMPLE 5 Monocyclopropyl diphenyl phosphate One mol of cyclopropanol is added dropwise with stirring to one mol of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of two mols of phenol in two mols of NaOH with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble monocyclopropyl diphenyl phosphate.

EXAMPLE 6 Monocyclopropyl paratolyl phosphate One mol of cyclopropanol is added dropwise with stirring to one mol of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./ Hg to remove hydrogen chloride. Without further purification this mixture is added drop- Wise at 0-5 C. to a saturated solution of two mols of paracresol in two mols of NaOH with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble monocyclopropyl paratolyl phosphate.

EXAMPLE 7 Monocyclopropyl phenyl tolyl phosphate One mol of cyclopropanol is added dropwise with stirring to one mol of POCl at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is filtered and the filtrate is added dropwise, without further purification, at 0-5 C. to a saturated solution of one mol of metracresol in one mol of NaOH with good stirring. The mixture is allowed to rise in temperature with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble monocyclopropyl phenyl metatolyl phosphate.

EXAMPLE 8 Dicyclopropyl cyclopropane phosphonate Three mols of cyclopropanol are added dropwise with stirring to one mol of cyclopropane phosphorus oxydichloride, at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dicyclopropyl cyclopropane phosphonate is collected.

EXAMPLE 9 Diphenyl cyclopropane phosphonate Three mols of phenol are added dropwise with stirring to one mol of cyclopropane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and diphenyl cyclopropane phosphonate is collected.

EXAMPLE 10 Dimetatolyl cyclopropane phosphonate Three mols of metacresol are added dropwise with stirring to one mol of cyclopropane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dimetatolyl cyclopropane phosphonate is collected.

5 EXAMPLE 11 Cyclopropyl metatolyl cyclopropane phosphonate One mol of cyclopropanol is added dropwise with stirring to one mol of cyclopropane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at -5 C. to a saturated solution of one mol of metacresol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble cyclopropyl metatolyl cyclopropane phosphonate.

EXAMPLE l2 Cyclopropyl phenyl cyclopropane phosphonate One mol of cyclopropanol is added dropwise with stirring to one mol of cyclopropane phosphorus oxydichloride at 25-35" C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble cyclopropyl phenyl cyclopropane phosphonate.

EXAMPLE l3 Dicyclopropyl benzene phosphonate Three mols of cyclopropanol are added dropwise with stirring to one mol of benzene phenyl phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dicyclopropyl benzene phosphonate is collected.

EXAMPLE 14 Dicyclopropyl toluene phosphonate Three mols of cyclopropanol are added dropwise with stirring to one mol of rnetatoluene phosphorus oxydichloride at 25-35 C. The temperature i slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dicyclopropyl toluene phosphonate is collected.

EXAMPLE l Cyclopropyl phenyl benzene phosphonate One mol of cyclopropanol is added dropwise with stirring to one mol of benzene phosphorus oxydichloride at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is washed, dried and distilled and cyclopropyl phenyl benzene phosphonate is collected.

EXAMPLE 16 Cyclopropyl metatolyl benzene phosphonate One mol of cyclopropanol is added dropwise with stirring to one mol of benzene phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./ Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of metacresol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is washed, dried and distilled and cyclopropyl metatolyl benzene phosphonate is collected.

EXAMPLE l7 Cyclopropyl tolyl toluene phosphonate One mol of cyclopropanol is added dropwise with stirring to one mol of rnetatoluene phosphorus oxydichloride at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 05 C. to a saturated solution of one mol of metacresol in one mol of sodiumhydroxide with good stirring. This mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is washed, dried and distilled and cyclopropyl tolyl toluene phosphonate is collected.

EXAMPLE 18 Cyclopropyl phenyl toluene phosphonte One mol of cyclopropanol is added dropwise with stirring to one mol of rnetatoluene phosphorus oxydichlon'de at Z5-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mitt/Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added drop wise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. This mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is washed, dried and distilled and cyclopropyl phenyl toluene phosphonate is collected.

EXAMPLE 19 Tolyl phenyl cyclopropane phosphonate One mol of metacresol is added dropwise with stirring to one mol of cyclopropane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. This mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is washed, dried and distilled and tolyl phenyl cyclopropane phosphonate is collected.

The compositions of my invention have high thermal stability apparently due to the presence of the cyclopropyl radical, high fire resistance, good lubricity, especially hydrodynamic lubricity, good boundary lubrication and good anti-wear, have ability to lubricate moving parts, particularly steel on steel, good viscosity and viscositytemperature properties, and are readily admixed with many additives.

It will be understood that the specific embodiments of my invention described above are intended to illustrate and exemplify my invention and are not necessarily intended as a limitation thereon and that modifications of my invention may be made.

I claim:

1. The phosphate and phosphonate esters represented by the formula (R R R )O O PO in which x may be one or zero, R is cyclopropyl, and R and R are cyclopropyl, phenyl or tolyl.

2. The chemical compound as defined in claim 1 which is tricyclopropyl phosphate.

3. The chemical compound as defined in claim 1 which is dicyclopropyl cyclopropane phosphonate.

4. The chemical compounds as defined in claim 1 which is dicyclopropyl phenyl phosphate.

5. The chemical compound as defined in claim 1 which 13. The chemical compound as defined in claim 1 which is dicyclopropyl benzene phosphonate. is monocyclopropyl tolyl benzenephosphonate.

6. The chemical compound as defined in claim 1 which 14. The chemical compound as defined in claim 1 which is dicyclopropyl tolyl phosphate. is monocylopropyl phenyl toluene phosphonate.

7. The chemical compound as defined in claim 1 which 5 is dicyclopropyl toluene phosphonate. References Clted 8. The chemical compound as defined in claim 1 which UNITED STATES PATENTS is monocyclopropyl diphenyl phosphate. 9. The chemical compound as defined in claim 1 which gg gii i 1S monocyclopropyl phenyl benzene phosphonate. 10

10. The chemical compound as defined in claim 1' which CHARLES R PARKER, primary Examiner is monocyclopropyl ditolyl phosphate.

11. The chemical compound as defined in claim 1 which SUTTO Assistant Examiner 1s monocyclopropyl tolyl toluene phosphonate 15 CL 12. The chemlcal compound as defined 1n claim 1 which is monocyclopropyl tolyl phenyl phosphate. 252 49-8 78; 260974 973 

